Note: Descriptions are shown in the official language in which they were submitted.
iZ95~38
~ 2 --
IMPROVEMENTS IN OR RELATING TO TEXTILE PRINTING AND DYEING
This invention relates to textile printing and
dyeing (hereinafter sometimes referred to as 'textile
colouring' or 'colouring').
There are currently two common methods of textile
printing, viz. direct and transfer paper printing. Of these
two methods of printing, direct printing is by far the more
prevalent form of printing because transfer paper printing
is limited to certain synthetic fibres and their mixtures
with cellulosic fibres and the effect of transfer paper
printing is different from the character of conventional
printing .
Direct colouring may take the form of pigment or
soluble dyestuff colouring. As is well known, direct
colouring with pigments as opposed to soluble dyestuffs,
involves physically binding the pigments to the fibre
surface using a binder, e.g. acrylic dispersion. Nowadays,
pigment printing is preferred because of its ease of
application e.g. the pigment preparations are incorporated
in a printing emulsion containing water, thickener,
emulsifier and various fixing agents, handle modifiers and,
optionally, solvents such as white spirit, the resultant
emulsion being printed onto the textiles, dried and heat
cured.
The disadvantages of pigment colouring are the
handle and the limited fastness to rubbing. Furthermore,
the pigment colouring process when used in dyeing as opposed
to printing has the further disadvantage of being limited to
pale shades only, because of limitations in build-up and
unsatisfactory rub-fastness properties, in depth generally
above 2% by weight fabric (b.w.f.) pigment preparation on
the fibre e.g. 20 g/l with 100% liquor pick up by weight of
fabric.
Printing of synthetic/cellulosic fibre mixtures
with soluble dyestuff mixtures has the disadvantage of high
cost and/or poor reproducibility whilst dyeing with soluble
```- 1;2~5~38
-- 3
dyes does not have the aforementioned disadvantage of
reproducibility to the same extent as printing.
Printing with soluble dyestuffs requires lengthy
processing, e.g. after printing and/or dyeing, the goods
need to be steamed or heat cured to fix the dyestuffs and
subsequently thickeners and unfixed dyestuffs and other
unreacted reagents used need to be removed in a separate
washing process. Similarly, conventional anti-migration
agents and unfixed dyestuff and other unreacted agents need
to be removed by washing from fabrics dyed by continuous
dyeing processes with soluble dyes by conventional methods.
Furthermore, printing of fibre mixtures, e.g.
synthetic/cellulosic fibre mixtures with soluble dyestuffs
requires the application of two or more dyestuff types,
specific for each fibre. Because of the different fixing
procedures for each dyestuff class, the process normally
suffers almost insurmountable disadvantages of high costs
and/or poor reproducibility.
Accordingly, it is a principal objective of this
invention to provide a process for direct colouring of
textile fibres which combines sùbstantially all the
advantages of both pigment and dyestuff colouring, but
substantially avoids the disadvantages of both types of
direct colouring.
It is another objective of this invention to
simplify the application, and particularly the selection, of
pigments and dyestuffs to suit various textile fibres and
mixtures thereof and hence to reduce the costs by reduction
of inventory and capital costs.
According to one aspect of the invention, there is
provided a process for direct coloring of textile fibers,
which process comprises (a) applying to conventionally
pretreated fibers a coloring mixture comprising: a cross-
linking agent consisting essentially of a solution of a
water insoluble partially precondensed hexamethoxymethyl
melamine (hereinafter referred to as "melamine" - see also
.. . .
`" lZ95~38
-- 4
attached Chemical Glossary of Trade Marks), said partially
precondensed melamine having 30-50% of said melamine in
precondensed form, in C4 8 glycol; one or more non-cationic
~olorants (e.g. pigments or dyestuffs and mixtures thereof);
and one or more acid donors; and (b) drying and fixing the
fibers.
The invention is applicable to a wide variety of
fibres but the invention is of particular advantage and
importance to fabrics consisting of 100% cellulosic fibres
and their blends of synthetic fibres, e.g. cotton,
cotton/polyester and polyester/rayon blends.
Preferably, the amount of melamine, glycol and acid
donor are in the ranges of 5 to 80g/l(g/kg), 5 to 120g/l
(g/kg) and l to 100g/l(g/kg) respectively based on the dye
liquor or print paste. More preferably, the above amounts
are 10 to 50g/l and lS to 50g/l respectively for the
melamine and the glycol.
It is essential that the melamine is water
insoluble. AS is well knowri, pure hexamethoxymethyl
melamine is a water soluble substance at room temperature.
To render the melamine water insoluble, it is slightly
self-condensed.
By necessity, polycondensed mixtures of nuclear
melamine are obtained, the complicated chemistry of which
could be stated in a simplified ~orm as follows:
Water insoluble melamine derivatives, such as
penta/hexamethoxymethyl melamine (P/H MOMM), by necessity
will be a mixture of polycondensed poly-nuclear melamine.
As all N-methylol compounds are in equilibrium with their
amines and free formaldehyde, there will always be a
possibility for formation of free amino groups which may
react with another N-methylol group and form a diaminal
(uron) N-N'-methylene compound. N-methylol compounds are
basically amino-semi-acetals and their methyl derivatives
will be amino-acetals.
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lZ95438
-- 5 --
The commercial, at room temperature insoluble,
melamine derivatives, described as essential for this
invention (such as Luwipal* 066 and Cymel** 303), therefore,
will be a mixture of insoluble poly-nuclear polycondensates,
free formaldehyde, methanol and P/H MOMM.
In contrast to water soluble melamines (such as
Luwipal* 068 and Kaurit* M70), which do not give
satisfactory results in this invention, products such as
Luwipal 066* are practically totally methylated (penta or
hexa). In the presence of aqueous acid (below about pH 5~,
the methyl group can be split off; the product becomes
soluble again and starts to react and condensate.
The production of such a poly condensed compound is
well-known and is generally as follows:
Melamine is reacted with formaldehyde and
acetylated with methanol. In the presence of acid catalysts
and in the absence of other functional groups, it condenses
with itself. Such a product is termed "technical"
hexamethoxymethyl melamine and is commercially available.
Generally, these mixtures comprise 50 to 70% by weight
hexamethoxymethyl melamine and also contain its condensation
products of 2 to 3 and up to 6 molecules of precondensed
melamine. For instance, a typical mixture may contain about
60~ by weight hexamethoxymethyl melamine, about 13% by
weight of the 2 to 4 molecular condensate and about 26% of
the 6 molecular condensate (e.g. Luwipal 066*).
Examples of C4 8 glycols are 2-methyl-butane-1,4-
diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol and
butane-2,3-diol, hexane-2,5-diol, pentane-1,5-diol and
neopentyl glycol. Preferably, the glycols used are 2-methyl
-pentane-2,4-diol, 2-methylpentane-1,5-diol and hexane-1,6-
diol.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
** Trade Mark of AMERICAN CYANAMID COMPANY
l~9S~339
For the dyeing of fibres, the acid donor is
preferably one or more saturated aliphatic Cq 6 dicarboxylic
acids and these are used in an amount of 1 to 5 g/l by
volume of dyebath. Examples of these acids are succinic,
glutamic and adipic acids, or commercially available
mixtures thereof (e.g. Eulysin*S). Alternatively, an
acrylic acid polymer or a heat saponifiable organic ester
such as Eulysin* WP, can be used as acid donor.
For the preparation of print pastes, the acid donor
is preferably a preparation of a high molecular weight
acrylic acid homopolymer or copolymer with acrlyamide and is
used preferably in an amount of 10 to 100 g/kg., more
preferably 10-50 g/kg by weight print paste. Its primary
function is however as a conventional thickener in the print
pastes.
The process according to the invention, can be
applied using dyestuffs or pigments, however, pigments,
anionic dyes, vat dyes and disperse dyes are preferred
(cationic dyestuffs generally do not work because of their
ionic nature). It may be advantageous to use blends of
different types of colourants, e.g. pigments with similar
colour dyestuffs, to obtain improved yield and fastness
properties.
Drying can be done separately from curing or
preferably in one operation. The curing reaction is very
fast provided the fibres can be dried very quickly.
Generally, curing is in the temperature range to 220C for a
period of 5 seconds to 4 minutes, preferably in the
temperature range 180 to 210C for a period of fifteen to
sixty seconds.
The dye liquor may contain further conventional
additives, such as anti-foam agents (e.g. Leophen M*),
dispersion agent (e.g. Setamol* WS), wetting agents (LEOPHEN
M*) and anti-migration agents (e.g. Primasol* AMK). Often
level dyeings are obtained particularly in the case of
pigments, without addition of conventional anti-migration
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
1295438
-- 7 --
agents; therefore a separate drying process in most cases is
not necessary and the fabrics can be dried at curing
temperatures. In fact, this is the preferred method.
The print pastes may, in addition, also contain
conventional thickening agents. In the process of this
invention, the thickening agents, e.g. polyacrylates, may
act as the acid donor. Furthermore, agents may be added to
the paste to improve the printing properties thereof e.g.
diethylene glycol. Optionally, emulsifiers ~e.g. Luprintol
PE*) and solvents with low or no aromatic content may also
be added.
Advantageously, silicone oils and vegetable oils,
optionally in the presence of urea, may also be added to the
print paste to enhance further the rub fastness and soft
handle.
It is preferred to use silicone oil which should
be, preferably, between 1,000 to 15,000 cps (centipoise)
and, more preferably, between 5,000 and 12,500 cps.
The preferred vegetable oil is castor oil (first
pressing).
Preferably, the amount of silicone oil (optionally
with urea) added ic 1-lOOg/kg print paste (each~, but more
preferably 10-60g/kg print paste (each), and more preferably
20-35g/kg print paste of silicone oil and 30-70g/kg urea.
According to a further aspect of the invention,
additions of small amounts of pigment binders are preferred
and have a beneficial effect on the resultant fastness
properties, particularly rub- and wash-fastness. The use of
a binder is particularly beneficial for 100% cotton goods or
their mixture, if they have not been sufficiently
pretreated. Binders are also sometimes beneficially added
for the purpose of preventinq anionic dyestuffs staining
white polyamide fibres during the first washing process.
ccordingly, the use (e.g. 10 to 100 g/kg by weight print
paste or dye liquor) of dispersions of cross-linked
copolymers of acrylic acid ester, acrylonitrile, acrylic
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
,
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1295~38
-- 8 --
acid and N-methylol methyl acrylamide (Helizarin Binder* TW)
were found to be beneficial.
In deep shades, lO to 100 g/kg, by weight print
paste or dye liquor, of binder was used, this having three
further benefits:
(a) increase in rub fastness; and
(b) assistance in fixation of the colourants on
100% cotton, especially if it is not well
pretreated (purified); and
(c) preventing staining of accompanying polyamide
fibres during washing.
Interesting and very elegant, pleasing and useful
print effects can be obtained by addition of silicate
particles (e.g. Iriodin**) to the print paste. This effect
can be further enhanced by curing the prints by heat
calendering (e.g. under 2 to 5 tons pressure plus heat),
instead of heat curing only.
According to another aspect of the invention, there
is provided an improved dye liquor or print paste comprising
a colourant (excluding cationic dyestuffs), an acid donor
and a cross-linking agent being a solution of a water
insoluble technical hexamethoxymethyl melamine in a C4 8
glycol.
According to a further aspect of the invention,
there is provided a cross-linking agent for use in
combination with a dye liquor or print paste being a
solution of a water insoluble technical hexamethoxymethyl
melamine in a C4 8 glycol.
According to yet a further aspect of the invention,
;~ 30 in the case of the use of a high sublimation fast Red
; disperse dyestuff (e.g. Celestren* Red 2G, CI Disperse Red
346) the cross-linking agent may simply be a C4 _ 8 glycol
~ In this situation, similar advantages and effects are
; obtainable to those in connection with the aforementioned
cross-linking agent.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
** Regd. Trade Mark of MERCK DARMSTADT
:
1295~38
According to another aspect of the invention, there
is provided an improved print paste comprising a colourant
(excluding cationic dyestuffs), one or more synthetic
thickening agents, a cross-linking agent being a solution of
a water insoluble technical hexamethoxymethyl melamine in a
C4 8 glycol and a silicone or vegetable oil, optionally in
the presence of urea.
According to a further aspect of the invention,
- there is provided a composition for enhancing the handle,
the rub resistance and water absorption of print pastes
comprising a mixture of silicone oil and urea.
According to yet a further aspect of the invention,
the improved print paste and resultant print properties can
be obtained by dispersing the water insoluble technical
hexamethoxymethyl melamine into the print paste (described
above) without previously dissolving it in a C9 8 glycol.
In this case, the print paste composition is limited to
containing, as a colourant, pigments or predominantly
pigments. Thus, according to this aspect of the invention,
there is provided a composition for enhancing the handle,
the rub resistance and wet fastener properties of print
pastes containing, as the colourant, pigments or
predominantly pigments, and a mixture of silicone or
vegetable oil and hexamethoxymethyl melamine (technical,
water insoluble) e.g. Luwipal 066*.
The C4 0 glycols appear to have several functions:
1) They dissolve and keep the melamine resin in
solution.
2) They provide hydroxyl groups for cross-linking with
functional groups inthe colourants, the melamine
resin and the fibres.
; 3) They can cross-link with the melamine forming the
melamine acetal, which in turn can cross-link via
; the hydroxy groups in the cellulose with similar
groups in the pigments or dyestuffs, depressing the
swelling of the fibre.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
~ ~95~38
-- 10 --
4) They improve the wet fastness, presumably by
forming insoluble complexes with the dyestuffs and
probably condensing with the hydroxyl groups in
cotton, The resultant dyestuff particles seem to
be present in highly crystallised form since quite
goods yields and brillance are obtained.
Similarly, the melamine resin reacts with various
functional groups, e.g. hydroxyl, carboxyl, amide, sulpho,
etc., commonly found in natural fibres, such as cotton, and
various dyestuffs, e.g. anionic dyestuffs.
It will be clear from the above that the invention
has the following advantages to offer to the user:
1. No wash-off necessary to remove unfixed dye bath
impurities (saving of energy and capital), compared
to conventional processes of dyeing and printing
100% cellulose or blends thereof with synthetic
fibres by using conventional (non-pigment) dyestuff
systems.
For example:
20 ~ Disperse/Vat dyestuffs applied to PE/Cotton
fabric PALANIL/INDANTHREN*
- ~isperse/Reactive dyestuffs applied to
PE/Cotton fabric; PALANIL/BASILEN*
- Reactant dyestuffs applied to PE/Cotton
fabric; CELLESTREN*
2. No causticizing pretreatment for the textile fabric
needed compared to some other dyestuff classes, in
other processes. Faster processing, e.g. curing
times which translates into capital saving.
30 3. Improved wet, light and rub fastness properties,
compared to some other dyestuff classes and
processes, e.g. compared to some direct dyestuffs,
acid dyestuffs and pigments in deep shades, etc.
Also the resistance to dry cleaning solvents is
improved.
- * Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
:
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129~38
4. Handle of fabric is at least comparable or improved
relative to conventional pigment prints or dyeing.
5. Good definition of prints.
6. Applicable to wide variety of fabrics, i.e. quite
non-fibre specific. Fibre reactive groups
cross-link whilst fibres without such groups e.g.
polyester, are bound by adhesion with the melamine
derivative resin on the one hand and the insoluble
dye complex on the other, e.g. salt formation with
the melamine and cross-linking
between dye, Cq 8 diols and melamine.
7. Non-staining or very little staining of polyamide
or wool fabric during washing.
8. Faster curing at 180-210C for as quick as 15 to 60
seconds.
9. Shorter fixation time in dry heat. This makes
fixation by dry heat, e.g. stenter/hot flue, very
economical.
Compared to pigment printing, the invention has the0 following advantages:
(a) Improved fastness to rubbing in deep shades;
(b) Depending on the chemical nature of the
dyestuff used, no binder or considerably
smaller amounts of binder and acid donor are
necessary.
It will further be appreciated from the above that
the present invention provides a process which is more
economical (Table I) than the prior art processes and which
provides improved reproducibility. Furthermore, the
30 colourants are most easily applied because only one colour
type can be used on the fibre mixtures. Moreover, there are
advantages for 100% cotton fabrics, namely more economical
dyestuffs can be used as there can be freer selection of
dyestuffs for their various properties, i.e. light fastness,
dry cleaning properties etc., irrespective of what the
intended original use for the dye was, i.e. dyes originally
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~zg~38
- 12 -
intended for completely other applications can now be used,
to obtain highly desirable results, e.g. anionic dyestuffs
originally intended to be used for the dyeing of leather can
be used for dyeing and printing of 100% cotton.
From the above, it follows that:
- Elegant combination of dyeing, printing, and
finishing processes are possible (Table II and
Example 12).
- Deep shades can be dyed rub- and wash-fast
utilizing the invention with most pigments;
basically most organic pigments are suitable.
Carbon black and iron oxide mixtures work also for
production of dark brown shades. Carbon black
works on its own for production of blacks.
- Most colour depths can be obtained, wherein
conventional pigment dyeing the depth is limited to
approximately 2% pigment preparation by weight of
fabric dyed.
- High sublimation disperse dyes, e.g. Cellestren*
when used in the invention, can be completely
fixed, with heat, making further processing, such
as washing rinsing and drying unnecessary.
- Similarly, disperse and vat dye mixtures, e.g.
Cottestren* can be fixed with heat alone by
utilising the invention.
- Anionic dyestuffs offer cost advantages in dark
shades, particularly Eukesolar* liquid/ Vialon*.
In light shades pigments are used preferably for
light fastness.
- The wash fastness of direct dyes are improved.
By using, in addition, the optional components of
silicone or vegetable oil, optionally in the presence of
urea, the following additional advantages are obtained:
1. The soft handle and the rub fastness is further
improved.
:
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
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1295~
- 13 -
2. The prints have improved absorbency.
3. Compared to conventional pigment prints, apart from
the softer handle and superior rub fastness, also lesser
amounts of binder dispersion are necessary. For example, in
the invention, never more tham 100 g/kg print paste is
necessary, whilst in conventional print paste up to 200 g/kg
are being necessarily used, Even so, by conventional
methods, one cannot obtain the same exceptionally high rub
fastness properties, compared to the invention. Binders
with low glass transition temperature can be used to
advantage, resulting in particularly soft handles. These
binders could not be used in conventional pigment printing
in deep shades as the high amounts needed would result in
"sticky" handle and poor rub fastness.
4. The invention is ideal for terry goods and delicate
jersey knit goods, as well as for fibre blends such as
acetate/cotton and Polyester/Rayon, however, it is of course
applicable and shows advantages on all kinds of textile
fibres.
5. The prints generally withstand 1000 rubs by the
AASC crockmeter method, whilst the standard test method is
10 rubs.
The invention will now be described and illustrated
in the following Examples which have been carried out,
unless otherwise indicated, by the following general
methods.
GENERAL METHODS**
Method I
Pretreatment I - for 100% cotton.
The loomstate cloths are saturated at 20-30 with a
liquor containing:
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
** The general methods of pre-treatment are by no
means mandatory, as any soundly practised
conventional pre-treatment method will suffice for
the purpose of this invention.
lZ9S~38
- 14 -
a detergent stable to alkalis e.g. Kieralon QL* 6.6 g/l
a wetting agent eg. Leophen M* 1.5 g/l
a Peroxide stabiliser and extraction agent
Prestogen EB 21 g/l
Caustic Soda (46% solution) 70ml/1
Hydrogen Peroxide 50% 50ml/1
After saturation, the fabrics are squeezed to a
pick up of approx. 80~ b.w.f., rolled up into a batch,
covered wityh polyethylene film and kept rolled for 16
hours. The fabric roll is then transferred t~ a jig machine
and treated with the following chemicals:
Caustic soda (46%) 15ml/1
oxidative starch degrading agent eg. Lufibrol O* 3 g/l
Kieralon OL 2 g/l
start running at 40C, raise over one end to 95~C, run two
ends at 95C, rinse with water for two ends at 95C, rinse
with fresh water for two ends at 40C, neutralise with cold
water containing dicarboxylic or carboxylic acids eg.
Eulysin S to pH 6-8.
After this treatmemt, the fabrics should be
reasonably free of sizing agents and impurities and should
have a neutral to slightly acid pH value.
Method II
Pretreatment for 50/50 Polyester Cotton.
Loomstate cloth, containing sizes, sighting colour
and other impurities, is saturated with the following
chemicals, liquor:
Alkali stable wetting agent eg. Leophen FK-1*7 g/l
Detergent, stable to alkali eg. Kieralon OL3 g/l
Peroxide stabiliser eg. Prestogen K* 10 g/l
Caustic soda (46%) 20ml/1
Sodium silicate 8 g/l
Oxidative starch degrading agent eg. Lufibrol O 9 g/l
Hydrogen Peroxide 50~ 44ml/1
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
12~5438
After saturation, the fabric is squeezed to a pick
up of 90% by weight fabric and steamed for 6 mins at
103-105C in saturated steam, eg. Arioli steamer.
After steaming, the fabric is washed off in open
width, through an open-width washing machine as follows:
1st Tank containing:
Sodium hydroxide flakes 15 g/1
Kieralon OL 6 g/l
Reductive extraction agent eg. Lufibrol Ks*4 g/l
Bath temperature 98C
2nd Tank containing:
Sodium hydroxide flakes 10 g/1
Kieralon OL 3 g/l
Lufibrol KB 4 g/l
Bath temperature 98C
3rd Tank containing:
3 g/1 Kieralon OL
Bath temperature 98C
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
~29543~
- 16 -
4th Tank containing:
Water at 98C
5th Tank containing:
Water, set with Eulysin S to pH 4-5
6th Tank containing overflowing cold water.
Method III
Pretreatment for nylon/cotton/acetate.
.
The loomstate fabric is desized on a jig machine with 1%
solution of starch degrading enzyme at 60C, pH 5-6.
After 8 hours reaction, the fabric is washed in a winch
machine with
Kieralon OL 2g/1 at 80C for 30 mins. followed by one rinse
with water at 45C, one rinse at room temperature.
'
The fabric is now ready for colouring according to invention.
Method IV
PreDaration of cross linkin~ a~ent solution
-~ The indicated amount of tech. hexamethoxymethyl melamine
is dissolved, by stirring at room temperature, into the
indicated amount of a suitable diol (see p.4). This solution
is now ready for use.
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1295438
- 17 -
Method V
Preparation of typical print paste
Into the prescribed amount of water (usually 600 to 800
g/kg) print paste emulsion is added by stirring at room
temperature the prescribed amounts of:
- Antifoam and/or wetting agent, plus
optionally urea
- Thickening agents
- Handle modifying agents, e.g. silicone and
vegetable oils and cross linking agent
solution
This mixture is homogenised by stirring at high speeds, e.g.
2,800 to 3,000 RPM, with a suitable mixing machine.
20 Finally, the prescribed amount of binder dispersion is added
by slow stirring - say 500 RPM.
To this mixture the prescribed amounts of colours are added
by slow stirring. The paste is made ready for printing, by
25 a final adjustment to constant printing viscosity, either by
addition of electrolyte solution or additional thickening
agent; and by straining through a mesh at least as fine as
the finest screen used for printing.
'
30 Method VI
Preparation of conventional print paste for pigment printing
on screen printing machines.
To the prescribed amount of water (usually 600-750 g/kg
print paste) at room temperature, is added by stirring, the
~; prescribed amounts of following ingredients:
~. ., " .
1295~38
_ 18 _
Ammonia (32%)
Antifoam
Thickeners
~andle modifiers and emulsifying emulsion
S Yield improving agents
1/2 of the prescribed amount of binder dispersion.
Into this mixture is emulsified at high speed 2800-3000 ~PM~
the prescribed amount of solvent eg. white spirit.
Finally, the second half of binder dispersion is added
under slow stirring.
To this preparation the prescribed amounts of colours are
added by slow stirring; the printpaste is ready for printing.
after adjusting to a constant printing viscosity, either
by addition of electrolyte solution or additional thickening
lS agents, and after straining through a mesh at least as
fine as the finest screen used in printing.
Method VII
-
Preparation of padding liquor.
To a smaller than prescribed amount o water, at room temp-
erature 25-30C, are added by stirring the prescribed amounts
of io11ouing ingredients:
:
" 12~S438
-- 19 --
Wetting Agent (non foaming)
Cross linking agent solution
Acid donor
Binder dispersion
S Colour
The mixture is adjusted to the prescribed volume with water
and stirred until homogeneous. It is strained into a padding
trough, through a fine sieve or cloth.
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lZ95438
- 20 -
EXAMPLE 1
A. Printing with 1:2 metal complex anionic disperse
dyestuff (Method I, II respectively for preparation; IV
and V for print paste preparation)
1,000 g of dyestuff printing paste was first prepared by
mixing the following materials:
Water Xg
(variable)
Mixture of Acid Violet CI 12196
and Acid Blue CI 12195 (EUKESOLAR** Navy R
conc. liquid) 20g
Tech. Hexamethoxymethyl Melamine (CYMEL 303*) 10g
2-methyl pentane-2,4-diol 20g
Polyacrylic Printing Binder (Helizarin
Binder TW) 30g
20 Dicarboxylix acids ~EULYSIN S) 2g
Polyacrylic thickener (LVTEXAL HP**) Yg
(variable)
1 0009
The above print paste composition was then applied
to 100% cotton and to 50/50 polyester cotton fabric through
a flat screen of 50 mesh using a magnetic roller squeegee on
a J. Zimmer flat bed printing machine, dried at 60C and
then cured for 3-4 minutes at 170C or, alternatively, 15-60
seconds at 190C, no wash-off being necessary.
* Trade Mark of AMERICAN CYANAMID COMPANY
** Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
:: :
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B. Dyeing with 1:2 metal complex anionic disperse
dyestuff - -
The same process as described or printing was used exceptthat the following composition (l,OOOg) was first prepared
as a padding liquor: (Method VII)
Water 749g
Mixture of Acid Violet CI 12196 and
Acid Blue CI 12195 (EUKESOLAR Navy R
conc. liquid) 25g
Non-foaming wetting agent (LEOPHEN M) lg
Polyacrylic Printing Binder (Helizarin TW)15g
Tech. Hexamethoxymethyl Melamine (CYMEL 303) lOg
2-methyl pentane-2,4-diol 40g
dicarboxilic acids (EULYSIN S) 2g
lOOOg
The above padding liquor was applied at 25C on a cotton and
polyester cotton fabric, 70% pick up; dried and cured like
the print (see above).
.
Good to very good fastness properties to light, ~ashing and
rubbing (wet and dry) were obtained.
:
`~ 1295438
_ 22 _
EXAMPLE 2
The following print paste was prepared as in Example 1 (Methods ]
IV, V):
Water 731g
Ammonia 3g
Anti foaming agent (DEFOAMER TP~) 3g
LUTEXAL HP 63g
2-methyl pentane-2,4-diol 15g
Tech. Hexamethoxymethyl Melamine 15g
(CYMEL 303)
Helizarin Binder TW 100g
Acid Black CI63 (EURESOLAR Black
R conc. liguid) 24g
EUKESOLAR Navy Blue R conc. liq. 36g
Acid Red CI226 (EUKESOLAR Red G) 5g
EUKESOLAR Yellow G 5g
lOOOg
20 metres of Cotton sheeting cloth was printed with the above
formulation on a flat bed BUSER printing machine, using a 80
mesh screen, dried at 110C and crease resist finished by foam
application of a crease resist glyoxal urea formaldehyde resin
e.g. FIXAPRET TX 205* and cured on a stenter for ll seconds at
190C; running speed 76m/min.
,; ~ ~ ''
. .
38
The following composition was used for the foam
resin application, through a Stork rotary screen applicator:
Water 761g
Acetic acid 90~ 2g
Polyethylene emulsion, e.g. Perapret PE 240* 60g
10 Fixapret TX 205 165g
Nekanil* TC 129 (non-ionic surface active,
foaming agent) lOg
Lutensit* TC KD (anionic surface active,
foaming agent) 29
1 0009
25% application b.w.f.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
12~5438
-- 24 --
EXAMPLE 3
Blue and Black prints were produced with a print paste prepared
as in Example 1, as follows:
Water Xg(variable)
Lutexal HP 50g
Diethylene Glycol lOg (to
improve
running
properties)
2-methyl Pentane-2,4-diol 15g
Tech. Hexamethoxymethyl Melamine (CYMEL 303) lOg
Eukesolar conc. liquid (variable)
lOOOg
Blue: 5g/kg Eukesolar Navy R conc. liquid, 15g/kg Luconyl
Blue 679 (Aqueous dispersion of Pigment Blue 15)
Black: 70g/kg Eukesolar Black R conc. liquid.
The above compositions were printed, dried, heat fixed
at 190C, 76m/min. (crease resist foam finished as in
Example 2), 11 sec. dwell time. Various other dark
prints were produced in this way, e.g. royal blue, dark
blue, dark brown, black on 100% cotton and 50/50
PE/cotton fabric.
1295438
EXAMPLE 4
B wn Print with 1:2 metal complex anionic disperse dyestuff
Paste prepared as in Example 1:
Water 699.4g
Defoamer* TP 10% solution lOg
Diethylene glycol 20g
Ammonia 32% (10% solu.) 50g
Lutexal HP 50g
Helizarin Binder TW lOOg
2-methyl pentane-2,4-diol 15g
Tech. ~examethoxymethyl Melamine
(CYMEL 303) 15g
Eukesolar Red G' conc. liquid 17g
Eukesolar Yellow RL liquid (Acid Yellow CI119) 4g
Eukesolar Black RL conc. liquid 18g
Eukesolar Navy Blue RL conc. liquid 1.6g
lOOOg
Printed and dried as in Example 1 on 100% cotton and 50/50 poly-
ester cotton fabric and cured for 60 seconds at 190C.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
3 29S~
- 26
EXAMPLE 5
Printing with 1:2 metal complex, water soluble anionic
dyestuffs
1000g print paste was prepared with the following composition:
Water 720g
1:2 metal complex dyestuff (Ortolar~Black RL
(Acid Black CI 63)
or Ortolan*Brown 3R (Acid Brown) 30g
2-methyl pentane-2,4-diol 30g
Tech. Hexamethoxymethyl Melamine 30g
(Luvipal 066)
Polyacrylic Thickeners (Lutexal HP) 80g
and Lutexal HVW) 10g
Polyacrylic Dispersion Printing Binder 100g
1~ Helizarin Binder TW
lOOOg
The composition was printed, dried and cured as in Example 1.
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
` 129~438
2 7 --
XAMPLE 6
Print on 100% and 50/50 ol ester/cotton fabric with
P Y _ _
l:2 metal complex disulphonate dyestuff
Print paste was prepared and printed as in Example 1, but with
the following composition:
Water 700g
Lutexal HP 60g
Helizarin Binder TW 100g
2-methyl pentane-2,4-diol 15g
Tech. Hexamethoxymethyl Melamine 15g
Silicone oil ** 200/12500 40g
Liquid paraffin 40g
1:2 metal complex disulphonate-Acid Red CI357
(Acidol Scarlet M-L*) 30g
1000g
-~ Regd Trade Mark of BASF Aktiengesellschaft
** Also known as "Siloxane 200/12500" manufactured
by DOW CORNING.
:1295438
28 --
EXAMPLE 7
Printing and Dyeing with Disperse Dyestuff on lOOD/o cotton and
50/50 polyester cotton fabric.
A. Printing was effected as in Example 1, with the following
print paste composition:
Water 715g
Lutexal HP 60g
Helizarin Binder TW 150g
Diethylene Glycol 20g
2-methyl pentane-2,4-diol l5g
Tech. Hexamethoxymethyl Melamine lOg
Disperse yellow CI 213
(Cellestren Yellow 5G) 30g
lOOOg
15 Printing and curing was carried out for 60 seconds at 190C (no
predrying).
B. Dyeing
The following padding liquor was prepared (Method VII):-
Water 834g
Leophen M 1g
2-methyl pentane-2,4-diol g0g
Tech. Hexamethoxymethyl melamine 15g
Helizarin Binder TW 20g
Eulysin WP lOg
Cellestren Yellow 5G' 30g
1 OOOg
`8
-- 2g --
EXAMPLE 7 B. continued:
The above liquor composition was applied to produce a 65%
pick-up by weight of fabric on 100% cotton and 50/50 polyester/
cotton fabric; curing for 60 seconds at 190C.
EXAMPLE 8
Dyeing on 100% cotton and 50/50 polyester/cotton fabric with
a red disperse dye
A pad dyeing was carried out as in Example 7B, with the followin~
pad liquor:
Water 699g
Leophen M lg
2-methyl pentane-2,4-diol 120g
Tech. HexamethoxymethY1 Melamine 60g
Eulysin WP lOg
Secondary Dispersion of Polyethylene Wax
(PERAPRET PE 240*) 30g
Cellestren Red 2G' 80g
lOOOg
: .
: ~ Regd Trade Mark of BAS~ Aktiengesellschaft
:: :
, ~
.,~,
~:
~,
, }~ ~ ....
129543~3
-- 30 --
EXAMPLE 9
Printing and dyeing with aqueous pigment dispersions
A. A print paste was prepared and printed on 100% cotton sheet-
ing; 50/50 polyester/cotton and 65/35 polyester cotton; as
in Example 1 with the following print paste:
Water 805g
Lutexal HP 30g
Silicone oil 200/12500 50g
Helizarin Binder TW 50g
Tech. Hexamethoxymethyl melamine 15g
Aqueous Dispersion of Pigment Red
(Helizarin Red GR) 50g
lOOOg
15 B. Dyeing with an aqueous pigment dispersion
The following pad liquor was prepared:
Water 835g
Leophen M lg
2-methyl pentane-2,4-diol 90g
Tech. Hexamethoxymethyl melamine lOg
Anti-migration agent e.g. Vitexal PFA* 2g
Eulysin S 2g
Helizarin Red GR 60g
lOOOg
Padded at 25C and 65% pick-up; curing for 60seconds at
1 90C .
-'~ Regd Trade Mark of BASF Aktiengesellschaft
1295438
EX/`I~PLE 10
Print on 50/50 Polyester/Cotton with 1:2 metal complex
sulphonamide dyestuff ? combined with 1:2 metal complex
disperse dyestuff
A print paste was prepared and printed as set out in the
General Methods with the following composition:
Water 805g
Lutexal HP 50g
Diethylene glycol , lOg
2-methyl pentane-2,4-diol 30g
Tech.hexamethoxymethyl melamine 30g
Eulysin WP Sg
Acid Red CI 226 (Eukesolar Red G conc.) 10g
Acid yellow CI 119 (Eukesolar Yellow R) 10g
Acid Blue/Violet Mix (Ortolan N.Blue BR) 40g
1000g
Printed on Zimmer magnetic table with 50 mesh flat screen and ther
cured 60 seconds at 190C.
~.
129~438
EXAMPLE 11
Print with aqueous pigment dispersion, combined with disperse dye
(General Methods I, II, III respectively, IV and V).
Print on 100% cotton, 50/50 polyester cotton and 50/50 acet-
ate/cotton fabric were prepared, printed and cured as in
Example 10 with the following composition:
Water 765g
Lutexal HVW lOg
Lutexal HP 40g
Helizarin Binder TW 80g
Diethylene glycol lOg
2-methyl pentane-2,4-diol 20g
Tech. Hexamethoxymethyl melamine 20g
Eulysin WP 5g
Aqueous dispersion of pigment green CI 36
(Luconyl green 915~) 40g
Disperse Yellow CI 213
(Cellestren yellow 5G) lOg
lOOOg
' ` 1295438
- 33 -
EXAMPLE 12 (~eneral ~ethods I, II, IV, VI and VII)
Combined dyeing/printing and finishing process technique, on 100
cotton and 50/50 polyester cotton light wei~ht sheeting fabrics.
A "TAUPE" and a "COCOA" shade was produced.
A. A padding liquor was prepared as in Example 9B, with the
following composition:
h~ater 911.5g
Leophen M lg
2-methyl pentane-2,4-diol 40g
Tech. Hexamethoxymethyl Melamine lOg
Lulysin S 20g
Vitexal PFA 2.5g
Heli~nn Binder TW 15g
lO~Og
15 To two lots of 100 litres, each of this padding liquor, the
following colour composition was added:-
Aqueous Dispersions of: Taupe Cocoa
Pigment Red (cf. Table IIï)
(Helizarin Pink BT) 0.16g 0.87g
20 Pigment Yellow 83
(Helizarin brilliant vellow RRT) 0.36g 0.62g
Helizarin Dk. Brown TT 1.36g 7. 5g
(mixture of carbon black & iron oxide)
Padding Liguor 1000g lOOOg
~ .
..:.,
l~9S~38
- 34 -
2 lots of fabric ~ere padded with each formulation respect_
ively, to 60% pick up, through a Kuesters pad mangle; the pad
dyeings were pre-dried to 12% residual moisture, by infra red
radiation.
Both fabrics were overprinted with the following pigment
print pastes:
Water 630g/kg - 803g/kg
Ammonia 32% 2g/kg - 2g/kg
Anti foam B (1:1 water)2g/kg - 2g/kg
Lutexal HP 26g/kg - 24g/kg
Emulsion FK 8520* 50g/kg - 40g/kg
Luprimol~* CW(colour intensifier)30g/kg - 24g/kg
White spirit lOOg/kg - 45g/kg
Helizarin Binder TW 150g/kg - 50g/kg
Alginate thickener 5% solutionlOg/kg - lOg/kg
Two designs, Gallery and Heathcote respectively, were printed
with 7 and 3 colourways respectively containing various amounts
(from lOOg/kg to 1.5g/kg), of combinations selected from two or
more aqueous pigment dispersions, from the following range:
HELIZARIN Black HDT, Blue RT, Red BBT, Violet RFKI, Yellow RRT,
green BT, scarlet B, Blue BT, Dark Brown TT.
.
A Buser flat bed machine using 60 and 80 mesh screens at
25m/min. running speed was used.
;~` 25 The prints were dried at 110 C 20 seconds; they were thencoated with a crease resist foam containing a standard glyoxal
ure~ formaldehyde resin formulation (Fixapret TX205~ ethod VII)
; through a Stork rotary screen and cured through a stenter at 190C
: for 11 seconds, running speed 76 m/min. Thus, the ground dyed
shade, the print and the crease resi5tant finish ~as cured in one
operation.
''
* M~nufactured by BASFAUSTRALIA LTD.
* Regd. trade mark of BASF AKllLNG~IS~T
,~
i`
12~5438
-- 35
The following fastness properties were obtained:
COCOA**/GALLER~''* TAUPE**/HEATHCOTE-~*
poly/cotton cotton poly/cotton cotton
Light 7 6 7 6
Rub Dry4 4 4/5 415
Wet3/4 3(print) 4/5 4/5
dyein~ rint dyeing/print dyeing/print dyeing/print
Machine
Wash
10 Domestic
Detergent
1 x wash 4/5 4/5 4/5 4/5 4/5 4/5 4/5 4/5
5 x wash 4, 4/5 3 4/5 4/5 4/5 3 4/5
Industrial
15 Detergent
Kieralon OL
plus soda ash
x S
; : washes 4 4/5 4/5 4/5
20 *: Trade/brand names of Sheridan Textiles (formerly
: Division of Pacific Dunlop Limited~.
These fastness properties were considered above average
for domestic sheeting fabrics widely sold in Australia.
:
, . . .
1295~38
EXAMPLE 13
A print was produced, as in Example 10, using the
following composition: -
Water 717 g
Ammonia 5 g
Antifoam* B 29 g
Lutexal HD 24 g
Luvipal 066 10 g
2 methyl Pentane-1,5 diol 80 g
Silicone Oil 200/12500 ** 40 g
Helizarin Binder TW 45 g
Cellestren Red 2G 35 g
Helizarin Red GR 15 g
1000 g
EXAMPLE 14
The following standard formulation was used to
check behaviour of a variety of colourants, when applied to
100~ cotton, by padding to 60% pick up and curing for 60
seconds at 200C.
Colourant Xg(variable)
Tech. Hexamethoxymethyl melamine 30 g
(Luvipal 066)
2-methyl pentane-1,5 diol45 g
alternatively
2-methyl pentane-2,4 diol45 g
alternatively
Hexane-1,6-diol 45 g
Leophen M 1.2 g
Eulysin S' 2.5 g
Helizarin Binder TW 20 g
1000 g
* Marketed by BASF AUSTRALIA
** DOW CORNING AUSTRALIA
;
~:
.. . .
1~9543~
- 37 -
The dyeings were soaped with an industrial detergent
e.g. 2g/1 Kieralon B*
for 10 min at 100C,
Rinsed and dried and tested for fastness properties.
The following properties were found (unless otherwise
indicated, the glycol used was 2-methyl-1,5-diol):
Regd. trade mark of BASF AKTIENGESELLSCHAFT
:
,
1295438
- 38 -
Light Wash Solvent Rubbing
Xeno- Test perchlor dry wet
test ISO 3
a) b) c) a) b) c)
5 5 g/l Helizarin
Brilliant Pink BT >6 4-55 4 4-54-55 4 4
soaped >6 4-55 4-54-54-55 4 3-4
5 g/l Helizarin
Brilliant Yellow RRT >6 4-55 4-54-54-55 3-43-4
soaped >6 4-55 4-54-54-55 3-43-4
5 g/l Helizarin
Dark Brown TT >6 3-44-54-54 4-55 4 3-4
soaped ~6 4 4-54-54-54-55 4 3-4
5 g/l Helizarin
Dark Brown TT
soaped >6 4 4-54-54 4-55 4 3-4
(2,4-diol) >6 4 4-54-54-54-55 4 3-4
5 g/l Helizarin
Dark Brown TT
soaped >6 4 4-54-54 4-55 4 3-4
(1,6-diol) >6 4-54-54-54-54-55 3-43
30 g/l Cellestren
Blue GG 5 4-54-54-52 4 4-52-32-3
soaped 5-fi 4-54-54-52-34 4-52-32-3
50 g/l Indanthren
Blue GCD >6 4 4-54-54 4-55 3 3
soaped >6 4-54-54-54 4-55 3 3
75 g/l Eukesolar
Black R liquid 4 4 4-52 4-53-44-54 3
soaped 4 3 4-51-24 3 4-54 2-3
Notes:
Light fastness is measured on scale 1-8 (8 being the best)
a) ~ change of shade on scale 1-5 (5 being the best)
b) = staining of cotton on scale 1-5 (5 being the best)
c) = staining of wool on scale 1-5 (5 being the best)
> means greater than
.~
; 35
1295438
- 39 -
EXAMPLE 15
Dyeing with disperse dyestuff (as per Example 1~ but with no
hexamethylene melamine) on 100% cotton and 50/50 polyester
cotton.
Water 669g
Leophen M lg
Primasol AMK 20g
Perapret PE 2/40 30g
2-methyl pentane 2,4-diol 200g
Cellestren Red 2G 80g
lOOOg
Pad 65~ pick up; dry 60C; cure 60 seconds at
200C.
1295438
-- 40 --
EXAMPLE 16
Printing ~ith solvent dyes
A print paste was prepared according to the general method
except that the solvent dyes were always predissolved in cyclo-
hexane.
Water 728g
Lutexal HP 30g
Helizarin Binder Th1 lOOg
2-methyl pentane-2,4 -diol 15g
Tech. Hexamethoxymethyl melamine 15g
(CYMEL 303)
Solvent Blue CI 21 1.25g
(Oracet Blue*)
Solvent Black CI 6 7g
(Savinyl Black BN**)
Solvent Brown CI 28 0.6g
(Savinyl Brown GLS**)
Solvent Red CI 122 0.6g
(Neozapon Red GE***)
,20 Cyclohaxanone lOOg
lOOOg
,
Printed, dried and cured as in Example 1.
-~ Reg Trade Mark of Ciba/Geigy
~;~ *~ Reg Trade Mark of Sandoz.
*** Reg Trade Mark of BASF Aktiengesel1schaft.
```` 1295438
-- 41 --
EXAMPLE 17
As Example 16 except that for the colourants the following
composition was used
Aqueous Dispersion of Pigment Yellow CI 2.5g/kg print/paste
(Luconyl yellow 098***)
Solvent Blue CI 38 2.5g/kg ". "
(Savinyl Blue 3GLS'*-L )
~ :
~ -
' ~
'. . , .:
12959~3~3
- 42 -
EXAMPLE 18
An improved colourant range is produced by
(a) mixing various selected colourants together (e.g.
450g CI Pigment Red 112 preparation plus 50g Disperse Yellow
213) at room temperature;
(b) Mixing separately, at room temperature, 475g
silicone oil 200/12500** and 2Sg hexamethoxymethyl melamine
(technical water insoluble-), resulting in a very smooth
paste, which is then added to mixture (a) and the components
are then mixed together at room temperature resulting in
colour (c).
Varying amounts of colour (c) are then added to a
print paste containing :
50 g/kg urea
x g/kg thickener e.g. Lutexal HP* (variable)
20-100 g/kg Acrylic Binder dispersion (e.g. Helizarin
Binder TW*)
9 g/kg Hexamethoxymethyl melamine (technical
insoluble) (e.g. Luwipal 066*)
1-35 g/kg Silicone oil 12/12,500
y g/kg water (variable)
Total - 1000g
EXAMPLE 19
Preparation of a typical colourant, provisionally termed
25 "Donanthren Yellow GC"
Pigment Yellow 164000g
Disperse Yellow 2131000g
Silicone oil 200/12500 47SOg
Hexamethoxymethyl melamine 250g
30 (technical, water insoluble)
(Luwipal 066) Total 10000g
The above ingredients were mixed together by simple
stirring at room temperature until a homogeneous product was
obtained. This composition is now ready for use in print
pastes as the "colourant".
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
** Made by DOW CORNING
;
129~438
- 43 -
EXAMPLE 20
A product, provisionally termed Product XPG, is
prepared by stirring together at room temperature, until
homogeneous,
98009 of hexamethoxymethyl melamine (technical, water
insoluble)
(Luwipal 066) and
2009 of silicone oil 200/12500
Total lOOOOg
This composition can be used as an additive to
print paste to enhance the softness of handle, the rub
resistance and wet fastness properties of said print paste.
EXAMPLE 21
lkg yellow print paste was produced by blending together at
room temperature with a variable speed stirrer (0-3000 RPM)
the following ingredients:
Water 750g
Polyacrylic thickner 40g
(Lutexal HP)
20 Urea 60g
Helizarin Binder TW lOOg
Product XPG (Example 20) lOg
Yellow colourant as in
Example 19 40g
Total lOOOg
This paste was printed on 100% cotton fine woven
fabric, 65/35 polyester/rayon, 50/50 polyester/cotton, non-
chlorinated wool, polyester/cotton/lycra knitted fabric and
100~ cotton towelling, through an 80 mesh flat bed screen,
:~ 30 on a Zimmer magnetic squeegee table, dried at 100C and
cured at 190C for 60 seconds. ISO wash test 3 gave a
rating of 4-5 and standard rub test by crock meter 10 rubs
was 5.
EXAMPLE 22
1 kg Black Print Paste
: The following composition was blended together at room
temperature, by stirring, until a homogenous paste was
~:
: ~
:
lZ9~438
- 44 -
obtained:
Water 717g
Polyacrylic Thickener
(Lutexal HP) . 40g
5 Urea 60g
Helizarin Binder TW 100g
Silicone 200/12,500 35g
Hexamethoxymethyl melamine
(technical, water insoluble)
10 (Luwipal 066) 10g
Helizarin Black HDT 20g
Helizarin Blue RT 9g
Helizarin br.Red BBT 4g
Cellestren* Yellow 5G 5g
1000g
This paste was printed on 100% cotton, and 65/35
polyester/rayon fabrics, through a 80 mesh flatbed screen,
on a Zimmer magnetic squeegee table, dried at 100C and
cured at 190C for 60 seconds.
EXAMPLE 23
The sàme procedure was used as in Example 21 but
using the following colours:
A) 45g/kg Aqueous preparation of Pigment Yellow 16
5g/kg Disperse Yellow 213
B) 23 g/kg Aqueous preparation of Pigment Orange 34
2 gm/kg Disperse Yellow 213
C) 25g/kg Aqueous preparation of Pigment Red 146
20g/kg Aqueous preparation of Pigment Yellow 83
5g/kg Disperse Yellow 213
D) 25g/kg Aqueous preparation of Pigment Blue 15:3
20g/kg Aqueous preparation of Pigment Blue 15:1
5g/kg Aqueous preparation of Pigment Violet 23
E) 10g/kg Aqueous preparation of Pigment Blue 15:3
10g/kg Aqueous preparation of Pigment Green 36
F) 25g/kg Aqueous preparation of Pigment Green 36
25g/kg Aqueous preparation of Pigment Green 7
* Regd. Trade Mark of BASF AKTIENGESELLSCHAFT
`~295438
- 45 -
G) 45g~kg Aqueous preparation of Pigment Violet 23
5g/kg Cellestren Red 2G*
H) lOg/kg Aqueous preparation of CI Pigment Yellow 83
12.5g/kg Aqueous preparation of CI Pigment Black 1
18.8g/kg Aqueous preparation of CI Pigment Blue
15:1
lOg/kg Aqueous preparation of CI Pigment Red 146
All gave the same good fastness properties as in
Example 21.
EXAMPLE 29
lkg matt white print paste, suitable to be printed on
coloured ground shades, was prepared by blending together
the following ingredients:
Water 555g
15 Polyacrylic thickener ~Lutexal HP) 40g
Acrylic Binder Dispersion
(Helizarin Binder TW) 150g
Silicone oil Siloxane DC 200/lZ500 50g
Hexamethoxymethyl melamine
(Luwipal 066) 5g
Aqueous preparation of rutile Titanium
Dioxide eg. Helizarin white RFK1200g
Total lOOOg
This paste was printed dried and cured as in
Example 21, but on 50/50 polyester/cotton sheeting fabric.
The same good fastness properties were obtained.
EXAMPLE 25
The same procedure was used as in Example 21 but
using the following formulation:
., ~
,
:
1295~38
- 46 -
Water 685g
Urea 60g
Thickener (Lutexal HP~ 40g
Hexamethoxymethyl melamine
(technical, water insoluble)
(Luwipal 066) 10g
Hexylene glycol 30g
Silicone oil 200/12500 35g
Helizarin Binder TW 100g
Disperse Yellow 213 30g
Pigment Red 146 10g
Total 1000g
The same good fastness properties as in Example 21
were obtained.
Very soft prints with very good fastness properties
were obtained.
All the materials produced in the above examples
(for which detailed fastness figures are not provided) were
tested, with emphasis on light, rubbing and wash fastness
and assessed visually.
The following methods, issued by the Standards
Association of Australia, were used to test all the samples
(except No. 14):
light fastnessAS 2001.4.21 (MVTF lamp)
rub fastnessAS 2001.4.3 (10x and 100 x
extended rubbing)
washingAS 2001.4.15
alsoISO 3 (International Standards
Organization)
dry cleaningAS2001.4.16
The materials produced in Example 14 were tested
according to the International Standards Organization
specifications. (It is to be noted that the AS standards
are based on the ISO specifications but adapted to the more
stringent climatic conditions prevailing in Australia and
required particularly for meeting Government contracts
requirements).
* Regd. Trade Mark of LASF AKTIENGESELLSCHAFT
` 1295438
- 46a -
In all cases the materials tested at least met and
often surpasses commercial standard requirements as
practised in Australia, Europe, U.S.A. and other developed
markets.
,~
i
,i
~`:
1295438
- 47 -
EXAMPLE 26
COMPARATIVE EXAMPLE - Illustrating Processing Advantages
Dyeing or printing of PE/Cotton with disperse
and VAT dyes / compared to Invention
Typical Process: Invention
Pre-Treatment:
10 Desizing Desiziny
Caustic Extraction (optional) Not required
Bleaching Bleaching
Washing Washing
Drying Drying
15 Dyeing
Pad Vat and Disperse Dyes Pad dyestuff and cross
linking agents, etc.
Dry *Dry
Heatfix, say 60 sec. 210C Heatfix, say 3-4
minutes, 170C, or
5-60 sec., 190C-210C
or HT-steam, say,
10-15 min. 185C
Pad with NaOH and Hydrosulphite
Steam, say 60 seconds. 102C
Rinse, oxidize, soap, rinse
Dry
*Optional, but precautions should be that excess liquor is
removed and does not cause migration/sagging.
Printing by conventional process
Similar to dyeing, but specialised steamer (Flash Ager)
required - not available or not installed in Australia at
present. With the invention, however, no such specialised
machinery is needed.
.. ,. '
.
129S~38
_ 48 -
EXAMPLE 27
Dyeing or printing of PE/Cotton with disperse and Reactive
Dyestuffs compared to Invention
-
Typical Process Invention
_
S Pretreatment
Desizing Desizing
Caustic Extraction Not required
Bleaching Bleaching
Washing Washing
10 Drying Drying
Dyeing
Pad Disperse eyes Pad dyestuffs and cross-linking
agent, etc.
Dry Dry
15 Heatfix, say 60sec. 215C HeaOfix, say 3-4 min.
170 C or 5-60 sec. 190C-210C
or HT steam gay 10-15
mins. at 185 C
Reduction clear (hydro-
sulphite/caustic) Not required
Wash Not required
Dry Not required
Repad with Reactives Not required
Fix Not required
25 Wash Not required
Dry Not required
Printing
Not practical - generally Highly practical - reproduceable
non reprod~ceable results results, since both fibres coloured
with same colourant
-` 12954~8
- 4g -
TABLE II
EXAMPLE OF ELEGANT PROCESS SEQUENCES
For dyeing a ground shade on P/C 50/50 light-weight
bed sheeting, followed by printing and resin finishing:
A. 1. Pad ground shade with invention and dry (e.g.
infra red pre-dry followed in one operation by
cylinder or hot flue drying).
2. Print with invention or pigments; dry in one
operation.
3. Apply crease-resist resin by foam and fix
ground shade, prints, and resin in one
operation, say at 190C, 15-17 seconds.
B. 1. Prepad colour/invention plus crease resist
resin, e.g. Fixapret COC from the same bath,
dry.
2. Print with invention or conventional pigment
paste.
3. Heat fix ground shade, resin and print in one
stenter pass.
- so - 12~5438
u u u o ~ o o o
~' ~ u O O u O ~ c ~ ~ æ ~ D
~:~ O O ~ ~ N
u u " o o a ~ ~ Z Z ~; ~ ' '
o
W zl ' E
O cl E ~
Zl _ E 0
W lW¦ c c , ~ o E
W¦ U - , C E'CE 'xo
t2 C ,~> S ,C bD ~ X v~ ~ ~ c
W N ' C .C~ ~-- ~, X ~ bD 0 ;~, C
1295438
- 51 -
TABLE III
Chemical Glossary of Trade Marks
Product Cas* No. Description
1. Lutexal HP 26100-47-0 ammonium acrylate, polymer
with acrylamide (C3H NO)X
64742-96-7 so~ven~ nap~ha (petroleum~
heavy aliphatic (mf not
specified)
104376-61-6 1,2,3-propanetriol,
polymer with
(chloromethyl) oxirane and
oxirane,momo-9-octadecenyl
ether,(z)
37295-87-1 isononylphenol,
ethoxylated (water) (C2H4
O)nCl5H240
15 2. Acrisint 311 9003-01-4 acrylic acid, homopolymer
(C3H4 2 )~
3. Eulysin WP 3002-18-4 triethanolamine triacetate
Cl 2 H2 1 N6
4. Primasol AMK 25085-02-3 acrylamide, polymer with
2 60dium acrylate
0 ~C3H ~O.C3H42 'Na)x
25g87-30-8 acrylic acid, polymer with
acrylamide, sodium salt
(C3H5NO~c3H402 )X ~XNa
5. Luprintol PE 82471-42-9 poly(oxy-1,2-ethanediyl),
: a-2-(2,4-DI=methyl-
phenoxy)-1-(2,4-dimethyl-
phenoxy)zmethyl ethyl-,
w-hydroxy- (mf not
specified)
;
~ 6. Helizarin
Brill.Pink BT 1047-16-1 C.I.** pigment violet 19
:~ Aqueous
~:: 30 preparation 22094-93-5 C.I. pigment yellow 081
based on : 6358-30-1 C.I. pigment violet 23
: * Chemical Abstracts System.
** Colour index as published by: Society of Dyers and
:35 Colourists V.K. and American Association of Textile
1 ~ : Chemists and Colourists.
i ~ ~
`: : :
"
.
` 1295438
- 52 -
7. Siloxane
200/12500 to
200/1000 63148-62-9 Siloxanes and silicones,
di-Me.
8. Luwipal 066 3089-11-0 1,3,5-triamine, N,N,N',
N',N'',N'' hexamethoxy-
methyl melamine
Cymel 303 hexakis (methoxymethyl)-
C15H30N6o~
Setamol WS 9084-06-4 napthalenesulfonic acid,
polymer with formaldehyde
sodium salt ~CloH8O3S.CH2
O)x.xNa
Ortolan B
Brown 3R C.I. acid brown 33
Cellestren
Yellow 5G
~iquid 64611-92-3 Butanamide,N-(2,4-
dimethoxyphenyl)-3-oxo-2-
[l2-(3-phenyl-1,2-4-
oxadiazol-5-yl)phenyl~A20]
Helizarin
Red GR 6535-46-2 C.l. pigment red 112
(aqueous preparation of)
3s
, ,,
